TECHNICAL REPORTS: SURFACE WATER QUALITY Assessment of Chlorophyll-a as a Criterion for Establishing Nutrient Standards in the Streams and Rivers of Illinois Todd V. Royer* Indiana University Mark B. David, Lowell E. Gentry, Corey A. Mitchell, and Karen M. Starks University of Illinois at Urbana-Champaign Thomas Heatherly II and Matt R. Whiles Southern Illinois University Nutrient enrichment is a frequently cited cause for biotic he Federal Clean Water Act requires states to identify impairment of streams and rivers in the USA. Eff orts are Timpaired water bodies and develop plans to reduce underway to develop nutrient standards in many states, but impairment. Nutrient enrichment, mainly with nitrogen (N) defensible nutrient standards require an empirical relationship between nitrogen (N) or phosphorus (P) concentrations and and phosphorus (P), is a frequently cited cause of impairment for some criterion that relates nutrient levels to the attainment streams and rivers (USEPA, 2000a). Nutrient loading can degrade of designated uses. Algal biomass, measured as chlorophyll-a the ecological integrity of streams and create human health (chl-a), is a commonly proposed criterion, yet nutrient–chl-a concerns. For example, the U.S. Environmental Protection Agency relationships have not been well documented in Illinois at a (USEPA) has set a drinking water standard of 10 mg NO –N L−1 state-wide scale. We used state-wide surveys of >100 stream 3 and river sites to assess the applicability of chl-a as a criterion to prevent methemoglobenemia. No drinking water standard for establishing nutrient standards for Illinois. Among all sites, exists for P; however, P enrichment can aff ect drinking water the median total P and total N concentrations were 0.185 and supplies by stimulating blooms of toxin-producing organisms, 5.6 mg L−1, respectively, during high-discharge conditions. such as cyanobacteria. Nutrient enrichment in streams stimulates During low-discharge conditions, median total P concentration algal growth with resulting impacts on habitat quality, trophic was 0.168 mg L−1, with 25% of sites having a total P of −1 ≥0.326 mg L . Across the state, 90% of the sites had sestonic relations, community structure, dissolved O2 concentrations, pH, chl-a values of ≤35 μg L−1, and watershed area was the best and aesthetic qualities (e.g., Miltner and Rankin, 1998). predictor of sestonic chl-a. During low discharge there was a Th e goal in developing nutrient standards for streams and riv- signifi cant correlation between sestonic chl-a and total P for those ers is to prevent a particular ecological condition (e.g., excessive ≤ ≤ −1 sites that had canopy cover 25% and total P of 0.2 mg L . algal biomass) by controlling the presumably limiting factor for Results suggest sestonic chl-a may be an appropriate criterion for the larger rivers in Illinois but is inappropriate for small rivers algal growth. Th e rationale behind nutrient standards is that eco- and streams. Coarse substrate to support benthic chl-a occurred logical impairment in nutrient-enriched streams is due, at least in <50% of the sites we examined; a study using artifi cial in part, to excess algal biomass and the eff ect of the excess bio- substrates did not reveal a relationship between chl-a accrual and mass on dissolved O2 defi cits via respiration and decomposition. N or P concentrations. For many streams and rivers in Illinois, However, the cause-and-eff ect relationship among nutrients, nutrients may not be the limiting factor for algal biomass due to the generally high nutrient concentrations and the eff ects algal biomass, and O2 defi cits is complicated by other environ- of other factors, such as substrate conditions and turbidity. mental factors that can maintain low algal biomass despite abun- dant nutrients (Dodds and Welch, 2000). For example, scouring, shading, grazing, and temperature can aff ect algal biomass inde- pendently of nutrient enrichment. Further complicating the de- velopment of nutrient standards is the fact that algae in streams and rivers occur in multiple forms, such as sestonic cells, epi- lithic biofi lms, and fi lamentous mats. Th ese various forms may diff er in their response to nutrient enrichment and the degree to Copyright © 2008 by the American Society of Agronomy, Crop Science which they are aff ected by other environmental factors. Society of America, and Soil Science Society of America. All rights Chlorophyll-a (chl-a) is a commonly used proxy for algal biomass reserved. No part of this periodical may be reproduced or transmitted and has been proposed as a criterion for identifying streams that fail to in any form or by any means, electronic or mechanical, including pho- tocopying, recording, or any information storage and retrieval system, without permission in writing from the publisher. Todd V. Royer, School of Public & Environmental Aff airs, Indiana Univ., Bloomington, IN 47405. Mark B. David, Lowell E. Gentry, Corey A. Mitchell, and Karen M. Starks, Dep. of Published in J. Environ. Qual. 37:437–447 (2008). Natural Resources and Environmental Sciences, Univ. of Illinois at Urbana-Champaign, doi:10.2134/jeq2007.0344 Urbana, IL 61801. Lowell E. Gentry, current address: Dep. of Crop and Soil Sciences, Received 28 June 2007. Michigan State Univ., East Lansing, MI 48824. Thomas Heatherly II and Matt R. Whiles, *Corresponding author ([email protected]). Dep. of Zoology and Center for Ecology, Southern Illinois Univ., Carbondale, IL 62901. © ASA, CSSA, SSSA 677 S. Segoe Rd., Madison, WI 53711 USA Abbreviations: chl-a, chlorophyll-a; DRP, dissolved reactive phosphorus; Q, discharge. 437 standards for N and P. To assist the state of Illinois with develop- ment of nutrient standards, we examined nutrient–chlorophyll relationships throughout the streams and rivers of the state. Because the state anticipates single, state-wide standards, our ap- proach was at the state-wide scale. Our goals included examina- tion of state-wide relationships between nutrients and chl-a as well as more mechanistically focused studies aimed at identifying environmental factors other than nutrients that may aff ect algal biomass in the streams and rivers of Illinois. Materials and Methods State-wide Surveys Quantifying the ecological response to nutrient enrichment across Illinois presents a challenge due to the diversity of stream types and land uses within Illinois. Illinois covers slightly more than 150,000 km2 and has a latitudinal gradient of 627 km, from 36°58′ N at the south to 42°30′ N at the northern boundary. Much of Illinois is rural and dominated by intensive row-crop agriculture with large inputs of N and P fertilizer (David and Gentry, 2000). Th e southern region of Illinois has more extensive tracks of hardwood forests and includes the Shawnee National Forest. Streams in the northeastern portion of the state are infl u- enced strongly by urbanization, with the Illinois River system re- ceiving the wastewater effl uent from the approximately 8 million people living in the greater Chicago region. Statewide, land cover is 76% agricultural, 12% forest, 6% urban, 4% wetland, and 2% other uses (Illinois Department of Agriculture, 2001). We conducted two state-wide surveys in 2004 designed to document conditions during distinct seasonal and hydrological conditions. A smaller state-wide survey was conducted in 2005 in conjunction with the artifi cial substrate study described below. Sites selected for the survey ranged in size from small, Fig. 1. Map of Illinois showing the major river networks and the wadeable streams to the large rivers of the state but did not distribution of the 138 sites used for the study. include the Mississippi, Ohio, or Wabash Rivers because these attain their designated use(s) due to nutrient loading (e.g., USEPA, rivers were not wadeable even at low discharge and could not 2000b). Because of the large number of streams and rivers that will be safely sampled from bridges. Most sites corresponded to likely require management intervention to reduce nutrient loading, locations used by Illinois EPA in their ambient water quality it is critical that the selected criterion be strongly associated with monitoring network. Th e goal in site selection was to identify a numerical water quality standards and attainment of designated representative group of sites that would allow for generalization uses (Reckhow et al., 2005). In Illinois, the strength of the relation- to the streams and rivers of the state as a whole. A complete ship between nutrients and chl-a has not been assessed at a state- listing of all sites is presented in Appendix A. wide scale, and the appropriateness of sestonic or benthic chl-a as a Th e fi rst survey examined 138 sites distributed across the state state-wide criterion for establishing nutrient standards is unknown. (Fig. 1) and was conducted from May to early July when most of Previous work in Illinois suggested that in wadeable agricultural the streams were at higher than basefl ow discharge (Q) but not streams sestonic chl-a was a poor indicator of eutrophic conditions fl ooded. An analysis of 103 of the sites that were gauged by the (Figueroa-Nieves et al., 2006; Morgan et al., 2006), but its applica- US Geological Survey indicated that, at the time of sampling, bility in larger rivers has not been examined. average discharge across the sites was 81% of the long-term mean Across large geographic regions, such as states or level III discharge for the month of May. For the second survey we revis- ecoregions (e.g., Woods et al., 2006), it is often diffi cult to ited 109 of the sites during September when the streams were at statistically relate nutrient concentrations to algal biomass (as basefl ow. In this paper we refer to the fi rst survey as the high-Q chl-a) due to spatial and temporal variations in hydrology, light, survey and the second survey as the low-Q survey.